Resinous products of the reaction of styrene with resins derived from bituminous coals of utah



iilatented Jan. 8, 1952 RESIN'OUS PRODUCTS OF THE REACTION OF STYRENEWITH RESINS DERIVED FROM BITUMINOUS GOALS OF UTAH Ernestl). Lee; Sparta,and Rupert J. S'chefbauer,

Jr., Hasbrouck. Heights, N. J assignors to Interchemical Corporation,New York, N. Y., a

corporation of Ohio No Drawing Application July 8, 1949, Serial No.103,754

12 Claims. 1

This invention relates to synthetic resins and particularly to suchresins formed by the conjoint polymerization of monomeric styrene with anatural resin such as the coal resins that are found in Utah coals;

Heretofore it has been known to polymerize styrene; either alone orconjointl'y with other polymerizable hydrocarbon monomers, especiallythose substances containing one' or more ethylenically unsaturatedgroups in the molecules, toform styrene polymers and copolymers. Thesepolymers and copolymers have particular properties such as chemicalresistance, water resistance, flexibility, etc. which would be verydesirable to impart to' protective coatings and inks. However, thesepolymers'have poor compatibility with the oil vehicles commonly used incoating and ink compositions. It is therefore an object of the presentinvention to provide a new resin containing copolymeri'zed' styrenewhich is compatible with oils and the usual varnish, lacquer,-

paint, and ink vehicles. Other objects of the invention will be apparentas the description of the invention proceeds.

The objects of our invention are attained as a result of our discoverythat monomeric styrene can be copolymerized with resins derived fromcoals such as are found in Utah to give copolymers that are compatiblewith the usual ink and coating composition vehicles. rene-coal resincopolymers are cooked into drying or semi-drying oils, such as tung oilor linseed oil, the resulting homogeneous oleoresinous vehicle can beused in the formulation of paints. varnishes, lacquers, inks, and thelike, in the usual manner. Films formed from such compositions possessgood flexibility, water resistance and chemical resistance.

In the practice of our invention we prefer to use inhibitor-freemonomeric styrene. Since styrene, as it is normally furnishedby themanufacturer, contains an inhibitor of' polymerization, weprefer toremove the inhibitor, asby distillation of the styrene from thenon-volatile inhibitor; This freshly distilled styrene is used directlyin our polymerization process.

The coal resin used in our invention can be characterized as a naturalresin occurring admixed with certain bituminous coals (notably that fromthe Utah coal" fields between Castlegate on the north and" Salina Canyonon the south) and consisting substantially of carbon (ca. 87- 88%) and.hydrogen (ca. Ill-12%), and having an acid number of the order of 6-8,and an iodine When these stY- This resin which occurs in Utah coals (upto about 10%) is commonly recovered by crushing the coal to an optimumtexture of fineness, effecting separation of a crude resin concentratefrom the crushed coal by froth flotation, and solvent extraction of thecrude resin concentrate with suitable solvent to obtain a soluble resinsubstantially free from coal and minerals (--100% One such process basedon this procedure yields a resin soluble in saturated petroleumhydrocarbon solvent (consisting essentially of hexanes, not more than25% of which is cyclic hydrocarbon). This resin, which will hereinafterbe referred to as the hexane-soluble resin can be used in the invention.Other grades or fractions of the coal resin may be used however. Forinstance, it is obvious that if the resin has been decolorizedduring itscourse of extraction from the coal, as by filtering the solution ofhexane soluble resin through fullers earth or activated heat treatedclay (disclosed in E1 D; Lee United States Patent 2,409,216, issuedOctober 15, 1946), the resulting decolorized resin can be used in theprocess of the invention. Also resins that have been obtained byextraction of the crude resin concentrate. with. other solvents can. beemployed in the present invention instead of the hexane soluble resin.For instance, the resin resulting from the extraction. of the resin withZ-methyl pentane (isohexane) as described. in our copending applicationSerial. No. 746,857, filed May 8,. 1947, now Patent No. 2,505,865, maybe used in the invention..

Advantageously, the coal resin is treated with an oxygen-containing gasprior to reacting it with. styrene. Such oxygen treatment can be carriedout for instance according to our copending United States patentapplication, Serial No. 17,375, filed March 26;. 1948, now Patent No.2,488,546, wherein a process comprising subjecting coal resin, spread inthin layers, to an oxygen-containing gas at temperatures of 5 to 15 0.below the melting point of the resin, is described and claimed.Treatment of the coal resin with an oxygen-containing gas followed byreaction with styrene yields a styrenated coal resin product which ismore compatible with drying oils, especially tung oil, in that clearervarnish films can be produced from the oleoresinous varnish preparedfrom the styrenated oxygenated resin that can usuallybe obtained usingcoal resin which has not been treated with oxygen.

The copolymerization of styrene with the coal resin preferably iscarried out out by heating a number of the order of -130 (Wijsmethod');solution of the coal resin or the oxidized coal resin and styrene in ahydrocarbon solvent in the presence of from 0.1 to 5% by weight, basedon reactants of an amphoteric metal halide catalyst such as aluminumchloride, boron trifiuoride and the like, and the organic solventcomplexes of such catalysts, e. g. boron trifluoride diethyl ethercomplex. The reactants are preferably polymerized in ratios of from 5 to50 parts styrene to 95 to 50 parts of coal resin. The new resins arecompatible with drying and semi-drying oils and contain enoughcopolymerized styrene to impart good chemical and water resistance, andflexibility to cured films. The varnishes obtained by cooking the resinsinto drying and semi-drying oils can be compounded with otherconventional varnish ingredients such as driers and pigments.

Suitable temperatures for conducting the polymerization are of the orderof 50 to 200 0., however, we prefer to carry out the polymerization attemperatures of 120 to 160 C.

Although we prefer to carry out the polymerization in a solvent such ashexane it is also possible to dispense with solvent entirely. Solventpolymerization is preferable chiefly because the temperature is moreeasily controlled.

Any suitable method may be used to purify the copolymer, i. e. toseparate solvent and/or catalyst from the polymer. For instance, thesolvent may be distilled off under atmospheric or reduced pressure.Catalyst is suitably removed by washing the solution of the resin withwater or aqueous or alcoholic alkali.

Copolymers formed by the process of the invention are soluble in oils,and hydrocarbon solvents such as petroleum hydrocarbons, both aliphaticand aromatic. The resins are insoluble in such solvents as alcohols,ethers, esters, and ketones.

The following examples, in which the parts are by weight, furtherillustrate the manner in which our invention may be practiced.

Example I Parts Styrene, inhibitor-free 110 Hexane soluble coal resin440 n-Hexane 220 Aluminum chloride, anhydrous 5 The coal resin wasdissolved in the styrene and hexane, the aluminum chloride then added,and the mixture heated to 75 C. for about '7 hours. The resultingsolution of copolymer was washed with a weak solution of ammoniumhydroxide in ethyl alcohol and then with water. The hexane solvent, andtraces of alcohol and water were removed by distillation to leave asolid dark colored resin.

Example II To a 60% solution of hexane soluble coal resin in monomericstyrene was added 1% of boron trifluoride-diethyl ether complex(containing about 37% boron trifiuoride) and the solution heated slowlyto about 170-175 C. (6 hours). The reaction mixture was then cooled to120 C. and enough toluene was added to make a 30% toluene solution. Fiveper cent by weight of calcium hydroxide was then added and the solutionwas stirred for 1 to 1 hours at 65 C., then filtered and the filtratevacuum distilled to remove the toluene. The yield of non-volatile resinwas 98%. This copolymer resin was compatible with such drying oils aslinseed oil and China-wood oil.

Example 111 varnishes of 25 gallon oil length with both tung oil andlinseed oil were made using the resins of the above examples. Thesevarnishes could be cut to any desired consistency with hydrocarbonsolvent and gave films having excellent flexibility, and chemical andwater resistance.

Example IV To a solution containing 150 parts by weight of oxygenatedUtah coal resin and 150 parts of styrene were added 6 parts by weight ofboron trifluoride diethyl ether complex (48% by weight of borontrifiuoride) Then the solution was heated gradually over a period of onehour and forty-five minutes to 150 C. Enough toluene was then added tomake a 35% solution. Fifteen parts by weight of calcium hydroxide werethen added and the mixture agitated one hour at 65 C. and then filtered.The filtrate was then vacuum distilled to remove the volatile solvent.The melting point of the resin remaining as residue was 100-105(capillary method).

The oxygen-treated coal resin used in Example IVwas obtained bysubjecting a hexane extracted coal resin, having a melting point of160-165 C., to air at 150 C. for 6 hours.

A tung oil varnish of 25 gallon oil length was prepared by cooking theappropriate amount of the resin obtained in Example IV with tung oil atvarnish cooking temperatures. Films of the finished varnish, when coatedon tin plate and baked for one-half hour at 350 C., were clear, hard,and compatible.

We claim:

1. A process for improving the properties of the hydrocarbon resinsderived from bituminous coals of Utah, consisting substantially ofcarbon and hydrogen, having an acid number about 6-8, and an iodinenumber about 100-130; which comprises heating 50 to parts of the coalresin with 50 to 5 parts of styrene at 50 to 200 C., in the presence ofcatalytic amounts of an amphoteric metal halide catalyst.

2. The process as claimed in claim 1, wherein the catalyst is borontrifiuoride.

3. A process for improving the properties of the hydrocarbon resinsderived from bituminous coals of Utah, consisting substantially ofcarbon and hydrogen, having an acid number about 6-8, and an iodinenumber about -130; which comprises heating 50 to 95 parts of thepartially oxidized coal resin admixed with 50 to 5 parts of styrene at50 to 200 C., in the presence of catalytic amounts of an amphotericmetal halide catalyst.

4. The process as claimed in claim 3, wherein the catalyst is borontrifiuoride.

5. The resinous product resulting from the heating of a mixture of 50 to95 parts of the hydrocarbon resin derived from bituminous coals of Utah,consisting substantially of carbon and r hydrogen, having an acid numberabout 6-8, and an iodine number about 100-103; and 50 to 5 parts ofstyrene at 50 to 200 C., in the presence of catalytic amounts of anamphoteric metal halide catalyst.

6. The resinous product as claimed in claim 5, resulting when thecatalyst is boron trifluoride. 7. The resinous product resulting fromthe heating of a mixture of 50 to 95 parts of the partially oxidizedhydrocarbon resin derived from bituminous coals of Utah, consistingsubstantially of carbon and hydrogen, having an acid number about 6-8,and an iodine number about 100-130; and 50 to 5 parts of styrene at 50to 200 C., in the presence of catalytic amounts of an amphoteric metalhalide catalyst.

8. The resinous product as claimed in claim 7,

1. resulting when the catalyst is boron trifluoride.

9. A varnish comprising a drying oil and a resinous product obtained byheating a mixture of 50 to 95 parts of the hydrocarbon"resin derivedfrom bituminous coals of Utah. consisting substantially of carbon andhydrogen having an 'acid number about 6-8, and an iodine number about100-130; and 50 to 5 parts pr styrene at 50 to 200 C., in the presenceof catalytic amounts of an amphoteric metal halide catalyst.

- when the catalyst is boron trifiuoride.

11. A varnish comprising a drying oil and a resinous product obtained byheating a mixture of to parts of the partially oxidized hydrocarbonresin derived from bituminous coals of Utah, consisting substantially ofcarbon and hydrogen, having an acid number about 6-8, and an iodinenumber about -130; with 50 to 5 parts of styrene at 50 to 200 0., in thepresence of catalytic amounts of an amphoteric metal halide catalyst.

12. A varnish as claimed in claim 11, resulting when the catalyst isboron trifiuoride.

ERNEST D. LEE. RUPERT J. SCHEFBAUER, JR.

REFERENCES CITED UNITED STATES PATENTS Name Date Lee et al. Feb. 15,1949 Number

1. A PROCESS FOR IMPROVING THE PROPERTIES OF THE HYDROCARBON RESINSDERIVED FROM BITUMINOUS COALS OF UTHA, CONSISTING SUBSTANTIALLY OFCARBON AND HYDROGEN, HAVING AN ACID NUMBER ABOUT 6-8, AND AN IODINENUMBER ABOUT 100-130: WHICH COMPRISES HEATING 50 TO 95 PARTS OF THE COALRESIN WITH 50 TO 5 PARTS OF STYRENE AT 50* TO 200* C., IN THE PRESENCEOF CATALYTIC AMOUNTS OF AN AMPHOTERIC METAL HALIDE CATALYST.